Process for permanently deforming keratinic fibers comprising an application step of an intermediate rinsing composition including a monovalent metallic cation or an ammonium salt and an organic acid

ABSTRACT

The invention concerns a process for permanently deforming keratinic fibers, in particular hair, which comprises:
         applying to the keratinic fibers a reducing composition, to reduce keratin disulfide linkages, the keratinic fibers being placed under mechanical tension before, during or after said application, preferably before, then   applying to the keratinic fibers an intermediate rinsing composition comprising at least one salt of a monovalent metallic cation and/or at least one ammonium salt, and at least one organic acid, said one or more monovalent salts not being one or more salts of said one or more organic acids present in the intermediate rinsing composition, and said one or more salts not being surfactants, then   applying to the keratinic fibers an oxidative composition in an oxidation fixing step, to recreate said linkages,   said process being free of any water rinsing step either between the reducing composition application step and the intermediate rinsing composition application step, or between the intermediate rinsing composition application step and the oxidative composition application step.

This application claims benefit of U.S. Provisional Application No. 60/904,174, filed Mar. 1, 2007, the contents of which are incorporated herein by reference. This application also claims benefit of priority under 35 U.S.C. § 119 to French Patent Application No. 0654853, filed Nov. 10, 2006, the contents of which are also incorporated herein by reference.

The present invention relates to a process for permanently deforming hair comprising a step of applying a reducing composition, a step of applying an intermediate rinsing composition comprising at least one monovalent salt and at least one organic acid, and a step of applying an oxidative composition, the application of the intermediate rinsing composition being neither preceded nor followed by a rinsing with water.

The most usual technique for obtaining a permanent deformation of hair consists, in a first step, in realizing the opening of disulfide links —S—S— of keratin (cystin) by means of a suitable reducing agent (reducing step) then, once the thus treated hair has been rinsed, generally with water, in reconstituting in a second step the said disulfide links by applying, on the hair previously placed under tension (rollers and others) or shaped or smoothed by other means, an oxidative composition (oxidation step, also known as fixing step) in order to finally impart the desired shape to the hair. This technique thus allows to indifferently realize either hair waving (permanent wave process), or hair uncurling or hair straighthening (smoothing process). The new shape imparted to the hair through a chemical treatment as above is highly durable in time and resists especially to the action of water washings and shampoos, contrary to simple classical temporary deformation techniques, such as hair setting.

The reducing compositions usable for implementing the first step of a permanent waving operation generally contain, as reducing agents, sulfites, bisulfites, alkyl-phosphines or preferably thiols. Among the latter, those currently used are the cystein and various derivatives thereof, the cysteamine and its derivatives, the thiolactic or thioglycolic acid, their salts as well as their esters, especially the glycerol thioglycolate.

The oxidative compositions necessary for implementing the fixing step are most often hydrogen peroxide based compositions.

However, such a technique is not fully satisfactory. In fact, this technique is very efficient to modify the shape of the hair, but is very damaging for the hair fibers.

Thus, for example, if the previously disclosed technique of permanently deforming hair are applied on hair having been previously subjected to an artificial coloring, it leads to a degradation or scouring of the artificial coloration.

Similarly, if a coloration is applied on permed according to the previously disclosed technique, the resulting color is very different from the color normally obtained on non permed natural hair.

On the other hand, water rinsing, between reduction step and oxidation step, also has the drawback of involving an over swelling of the keratinic fibers. Such an over swelling impairs the cosmetic properties of keratinic fibers, in particular the softness, the gloss, the touch, as well as the smoothing or disentangling ability.

Finally, generally, the reducing composition has an alkaline pH due to the presence of one or several alkaline agents. After application of the reducing composition, there is generally an abundant water rinsing to eliminate any trace alkaline residues. This results in an increase of water consumption and spoil of the environment.

There is known from document U.S. Pat. No. 6,173,117 a permanent deformation process of hair which aims to avoid excessive hair curling and which comprises applying on hair a reducing composition, a pause time, optionally rinsing with water, applying an intermediate aqueous acid composition comprising a salt, preferably divalent, an aliphatic organic acid and a betain, placing the hair under tension, a further pause time, then applying an oxidative composition.

There is also known from document EP 443 356 a permanent deformation process of hair comprising a reduction step, an intermediate rinsing step and an oxidation step. The intermediate rinsing step is performed using an aqueous solution such that at any time during rinsing, the fiber diameter does not increase more than 30% with regard to the fiber diameter at the end of the reducing step. In particular, the aqueous solution used in the intermediate rinsing step is a sodium chloride aqueous solution.

A permanent deformation process of hair is also known from FR 2 721 823 which comprises an application step on the hair of an acid composition containing a carboxylic acid and/or one of its associated salts, an optional water rinsing step, an application step of a reducing composition, the placement of the hair under tension being effected before, during or after said reducing composition application or before the application of the acid composition, a water rinsing step, then an application step of an oxidative composition.

A permanent deformation process of keratinic materials is known from FR 2 718 351 which comprises an application step on the hair of a reducing composition, the placement under tension of the hair being effected before, during or after said application, a water rinsing step, and an application step of an acid composition comprising a carboxylic acid, said process being free of a fixing chemical step through oxidation.

A permanent deformation process of hair is finally known from EP 0 880 916 in which hair are rolled on rollers, a reducing composition is applied on the rolled hair, and lets to act, the curls are treated, without a previous water rinsing, with an intermediate acid and aqueous rinsing composition containing an aliphatic organic acid and a hair care and conditioning component, the possible excess of liquid on the curls is withdrawn by dabbing, one lets act, there is an optional water rinsing, hair are treated before and/or after withdrawal of the rollers by means of an oxidant base fixing agent, and after an action period, the fixing agent is withdrawn from the hair through water rinsing or through washing with a shampoo. The intermediate rinsing composition may contain a salt such as sodium cetylstearyl sulfate or dimethyl diallyl ammonium chloride.

None of the disclosed processes leads to a totally satisfactory permanent deformation process regarding the above mentioned problems.

There is thus a need for a permanent deformation process of keratinic fibers which does not degrade the artificial coloring of hair and does not impair the cosmetic properties, such as. the softness, the gloss, the touch, as well as the smoothing or disentangling ability.

Applicant has now discovered that one or more of the prior art problems can be solved by a process for permanently deforming keratinic fibers which comprises a reduction step, the keratinic fibers being placed under mechanical tension before, during or after said reduction step, then an intermediate rinsing step by means of a composition comprising at least one salt of a monovalent metallic cation and/or at least one ammonium salt, and at least one organic acid, said one or more salts not being one or more salts of said one or more organic acids present in the intermediate rinsing composition, and said one or more salts not being surfactants, then an oxidation step, said process being free of any water rinsing step either between the reduction step and the intermediate rinsing step, or between the intermediate rinsing step and the oxidation step.

The object of the invention is thus a process for permanently deforming keratinic fibers, in particular hair, which comprises:

an application step on the keratinic fibers of a reducing composition, to reduce keratin disulfide linkages, the keratinic fibers being placed under mechanical tension before, during or after said application, preferably before, then

an application step on the keratinic fibers of an intermediate rinsing composition comprising at least one salt of a monovalent metallic cation and/or at least one ammonium salt, and at least one organic acid, said one or more monovalent salts not being one or more salts of said one or more organic acids present in the intermediate rinsing composition, and said one or more salts not being surfactants, then

an oxidation fixing step, to recreate said linkages, through application on the keratinic fibers of an oxidative composition,

said process being free of any water rinsing step either between the reducing composition application step and the intermediate rinsing composition application step, or between the intermediate rinsing composition application step and the oxidative composition application step.

By ammonium salt there is meant in the present invention a salt of NH₄ ⁺.

According to a preferred embodiment, the reducing composition is let to act for 5 to 60 minutes, preferably for 5 to 30 minutes.

The reducing composition used in the process of the invention generally comprises, in a cosmetically acceptable medium, at least one reducing agent selected from reducing agents of formula:

H(X′)_(q)(R′)_(r)

In which X′ represents P, S or SO₂, q is 0 or 1, r is 1 or 2 and R′ is a (C₁-C₂₀)hydrocarbon radical, linear, branched, saturated, unsaturated, optionally interrupted by an hetero atom, and optionally bearing substituents selected from a hydroxy group, a halogenated group, an amine or a carboxy group, a ((C₁-C₃₀) alkoxy)carbonyl group, an amido group, a ((C₁-C₃₀)alkyl)amino carbonyl group, a (C₁-C₃₀)acyl)amino group, a mono or dialkylamino group, a mono or dihydroxylamino group, or one of its salts in combination with a base.

Preferably, the one or more reducing agents are selected from thioglycolic acid, thiolactic acid, glycerol monothioglycolate, cysteamine, N-acetyl-cysteamine, N-propionyl-cysteamine, cystein, N-acetyl-cystein, thiomalic acid, panthetein, 2,3-dimercaptosuccinic acid, N-(mercaptoalkyl)-ω-hydroxyalkylamides, N-mono or N,N-dialkylmercapto-4-butyramides, aminomercapto-alkylamides, derivatives of N-(mercaptoalkyl)succinamic acids and N-(mercaptoalkyl)succinimides, alkylamino mercaptoalkylamides, the azeotropic mixture of 2-hydroxypropyl thioglyconate and (2-hydroxy-1-methyl)ethyl thioglycolate, mercaptoalkylaminoamides, N-mercapto-alkylalkanediamides and the derivatives of formamidine sulfinic acid, and their salts.

The one or more reducing agents generally represent 0.05 to 30%, preferably 1 to 20%, better 4 to 11% by weight based on the total weight of the reducing composition.

In order to improve the cosmetic properties of hair fibers or still to weaken or avoid their degradation, the reducing composition used in the process of the invention can also include one or more cosmetically active ingredients.

This or these active ingredients are generally selected from volatile or non volatile silicones, linear or cyclic, aminated or not, cationic, anionic, non ionic or amphoteric, polymers, peptides and their derivatives, protein hydrolysates, fatty compounds, natural and synthetic waxes, and in particular fatty alcohols, swelling or penetration agents or agents allowing increasing the efficiency of the one or more reducing agents, as well as other active compounds such as anionic, cationic, non ionic, amphoteric or zwitterionic surfactants, anti-drop agents, anti-dandruff agents, natural or synthetic thickeners, associating or not, suspension agents, chelating agents, opacifying agents, colorants, solar filters, vitamins and provitamins, mineral, vegetable or synthetic oils, as well as perfumes and preservative agents, and their mixtures.

As chelating agents, there may be cited for example the pentasodium salt of the diethylene triamine pentaacetic acid.

As surfactants, there may be cited for example the oxyethylenated oleic alcohol with 20 moles of ethylene oxide, the mixture of cocoyl amidopropryl betaine/glyceryle mono-laurate, the lauryl dimethyl amine oxide, the behenyl trimethyl ammonium chloride, the stearylic alcohol, the glyceryle mono distearate, the monoethanolamide of the alkyl(C13/C15 70/30 50% linear) ether (2 OE) carboxylic acid, the mixture of cetylstearylic alcohol/oxyethylenated (30 OE) cetylstearylic alcohol and the oleocetyl dimethyl hydroxyethyl ammonium chloride.

As conservative agent, there may be cited for example the sodium salicylate.

As opacifying agent, there may be cited for example the vinylpyrrolidone/styrene copolymer.

As fatty compound, there may be cited for example, vaseline.

As thickener, there may be cited for example the oleic alcohol and the cetylic alcohol.

In the meaning of the present invention, the term “cationic polymer” relates to any polymer containing cationic groups and/or groups that are ionisable into cationic groups.

The cationic polymers possibly present in the reducing composition used in the process of the invention can be selected among all those already known per se as improving the cosmetic properties of hair, namely those disclosed in patent application EP-A-337 354 and in French patents FR-2 270 846, 2 383 660, 2 598 611, 2 470 596 and 2 519 863.

The preferred cationic polymers are selected among those which contain units having primary, secondary, tertiary and/or quaternary amine groups that can, either be part of the polymer main chain, or be born by a side substituent directly linked to the main chain.

The used cationic polymers generally have a weight average molecular weight ranging from 500 to 5.10⁶ about, and preferably ranging from 10³ to 3.10⁶ about.

Among the cationic polymers, there may be more particularly cited the polymers of the polyamine, polyaminoamide and poly(quaternary ammonium).

These are known products. They are notably disclosed in French patent no 2 505 348 or 2 542 997. Among these polymers, there may be cited:

(1) Homopolymers or copolymers derived from acrylic or methacrylic esters or amines and including at least one of the units of the following formulas (I), (II), (III) or (IV):

in which:

R₃, identical or different, represent a hydrogen atom or a CH₃ radical;

A, identical or different, represent an alkyl group, linear or branched, having 1 to 6 carbon atoms, preferably 2 to 3 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;

R₄, R₅, R₆, identical or different, represent an alkyl group, having 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group having 1 to 6 carbon atoms;

R₁ et R₂, identical or different, represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms and preferably methyl or ethyl;

X is an anion derived from a mineral or organic acid such as a methosulfate anion or a halogenide as chloride or bromide.

There may be cited in particular the homopolymer of ethyl trimethyl ammonium methacrylate chloride.

The polymers of family (1) may further contain one or more units deriving from comonomers that can be selected in the family consisting acrylamides, methacrylamides, diacetones acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower (C₁-C₄) alkyls, acrylic or methacrylic acids or their esters, vinyllactames tels such as vinylpyrrolidone or vinylcaprolactame, vinylic esters.

Thus, among polymers of family (1), there may be cited:

the copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or a dimethyl halogenide, such as the one sold under the name HERCOFLOC® by HERCULES,

the copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride disclosed for example in patent application EP-A-080976 and sold under the name BINA QUAT P100® by CIBA GEIGY,

the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate sold under the name RETEN® by HERCULES,

the vinylpyrrolidone/acrylate or methacrylate dialkylaminoalkyl copolymers, quaternized or not, such as the products sold under the name “GAFQUAT®” by ISP as for example “GAFQUAT 734®” or “GAFQUAT 755®” or the products named “COPOLYMER 845, 958 et 937”. These polymers are precisely disclosed in French patents 2,077,143 et 2,393,573,

the dimethyl amino ethyl methacrylate/vinylcaprolactame/vinylpyrrolidone terpolymers such as the products sold under the name GAFFIX VC 713® by ISP,

the vinylpyrrolidone/methacrylamidopropyl dimethylamine copolymer commercialized in particular under the name STYLEZE CC 10® by ISP,

and the copolymers vinylpyrrolidone/quaternized dimethylaminopropyle methacrylamide such as the product sold under the name “GAFQUAT HS100®” by ISP

(2) The cellulose ether derivatives having quaternary ammonium groups as disclosed in French patent 1 492 597, and in particular the polymers commercialized under the names “JR” (JR 400, JR 125, JR 30M) ou “LR” (LR 400, LR 30M) by Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as hydroxyethylcellulose quaternary ammonium being reacted with a trimethylammonium group substituted epoxide.

(3) The cationic cellulose derivatives such as cellulose copolymers or cellulose grafted with a hydrosoluble quaternary ammonium monomer, and disclosed notably in U.S. Pat. No. 4,131,576, such as hydroxyalkyl celluloses, like hydroxymethyl-, hydroxyethyl- or hydroxypropyl-celluloses grafted in particular with a salt of methacryloylethyl trimethylammonium, methacrylimidopropyl trimethylammonium, dimethyl-diallylammonium.

Commercialized products according to this definition are more particularly the products sol under the name “Celquat L 200®” and “Celquat H 100®” by National Starch.

(4) The cationic polysaccharides cationics disclosed more particularly in U.S. Pat. Nos. 3,589,578 and 4,031,307 such as guar gums including cationic trialkylammonium groups. There is used for example guar gums modified by a salt (for ex. chloride) of 2,3-epoxypropyl trimethylammonium.

Such products are commercialized in particular under the tradenames JAGUAR C13 S®, JAGUAR C 15®, JAGUAR C 17® or JAGUAR C162® by MEYHALL.

(5) The polymers constituted of piperazinyl units and divalent alkylene or hydroxyalkylene with straight or branched chains, optionally interrupted by oxygen, sulfur, nitrogen atoms or by aromatic cycles or heterocycles, as well as oxidation and/or quaternization products of these polymers. Such polymers are notably disclosed in French patents 2,162,025 and 2,280,361.

(6) The water soluble polyaminoamides prepared in particular by polycondensation of an acid compound with a polyamine; these polyaminoamides can be crosslinked by an epihalohydrine, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrine, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halogenide or still by an oligomer resulting from the reaction of a bifunctionnal compound which is reactive with a bis-halohydrine, a bis-azetidinium, a bis-haloacyidiamine, an alkyl bis-halogenide, an epilhalohydrine, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mole per amine group of the polyaminoamide; these polyaminoamides can be alkylated or quaternized when they bear one or several tertiary amine functions. Such polymers are notably disclosed in French patents 2,252,840 and 2,368,508.

(7) The polyaminoamides derivatives resulting from the condensation of polyalkylenes polyamines with polycarboxylic acids followed by an alkylation by means of bifunctionnal agents. For example one can cite the adipic acid-dialkylaminohydroxyalkyldialkylne triamine polymers in which the alkyl radical includes 1 to 4 carbon atoms and is preferably methyl, ethyl, propyl. Such polymers are notably disclosed in French patent 1,583,363.

Among these derivatives, one can cite more particularly the adipic acid/dimethylaminohydroxypropyl/diethylene triamine polymers sold under the name “Cartaretine® F, F4 or F8” by Sandoz.

(8) the polymers obtained by reacting a polyalkylene polyamine including two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids having 3 to 8 carbon atoms. The molar ratio between the polyalkylene polylamine and the dicarboxylic acid ranging from 0.8:1 and 1.4:1; the resulting polyaminoamide being brought to react with the epichlorhydrine in a molar ratio of epichlorhydrine to the secondary amine group of the polyaminoamide ranging from 0.5:1 et 1.8:1. Such polymers are notably disclosed in American U.S. Pat. Nos. 3,227,615 and 2,961,347.

This type of polymers are commercialized in particular under the name “Hercosett 57®” by Hercules Inc. Or under the name “PD 170®” or “Delsette 101®” by Hercules in the case of adipic acid/epoxypropyl/diethylene-triamine.

(9) The alkyl diallyl amine or dialkyl diallyl ammonium cyclopolymers such as homopolymers or copolymers having, as main chain constituents, units of formulas (V) or (VI):

formulas in which k and t are equal to 0 or 1, the sum k+t being equal to 1; R₉ represents a hydrogen atom or a methyl radical; R₇ and R₈, independently from each other, represent an alkyl group having 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl has preferably 1 to 5 carbon atoms, a lower (C₁-C₄) amidoalkyl group, or R₇ and R₈ can, jointly with the nitrogen to which they are linked, represent heterocycle groups, such as piperidinyl or morpholinyl; R₇ and R₈ independently from each other preferably represent an alkyl group having 1 to 4 carbon atoms; Y⁻ is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. These polymers are notably disclosed in French patent 2,080,759 and in its addition certificate 2.190.406.

Among the above defined polymers, there may be more particularly cited the homopolymer of dimethyldiallylammonium chloride sold under the name “Merquat 100®” by Calgon (and its low weight average molecular weight homologs) and the diallyldimethylammonium chloride and acrylamide commercialised under the name “MERQUAT 550®”.

(9) The quaternary diammonium polymer including repeating units of formula:

formula (VII) in which

R₁₀, R₁₁, R₁₂ et R₁₃, identical or different, represent aliphatic, alicyclic, or arylaliphatic radicals having 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or further R₁₀, R₁₁, R₁₂ and R₁₃, together or separately, form with the nitrogen atom to which they are heterocycles optionally including a second heteroatom other than nitrogen or else R₁₀, R₁₁, R₁₂ and R₁₃ represent a C₁-C₆ linear or branched alkyl radical substituted by a nitrile, ester, acyle, amide or —CO—O—R₁₄-D or —CO—NH—R₁₄-D group where R₁₄ is an alkylene and D a quaternary ammonium group;

A1 et B1 represent polymethylene groups having 2 to 20 carbon atoms that can be linear or branched, saturated or unsaturated, and possibly containing, linked to or interspersed in the main chain, one or several. aromatic cycles, one or several oxygen, sulphur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

X⁻ is an anion derived from a mineral or organic acid;

A1, R₁₀ and R₁₂ can form with the two nitrogen atoms to which they are linked a piperazine cycle; furthermore when A1 is an alkylene or hydroxyalkylene radical, linear or branched, saturated or unsaturated, B1 can also be a —(CH₂)n-CO-D-OC—(CH₂)n-group in which D is:

a) a glycol rest of formula: —O-Z-O—, where Z is a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas:

—(CH₂—CH₂—O)x-CH₂—CH₂

—[CH₂—CH(CH₃)—O]y-CH₂—CH(CH₃)—

wherein x et y are integer from 1 to 4, representing a defined and sole polymerization degree or any number from 1 to 4 representing an average polymerization degree;

b) a bis-secondary diamine rest such as a piperazine derivative;

c) a bis-primary diamine rest of formula: —NH—Y—NH—, or Y represents a linear or branched hydrocarbon radical, or else the bivalent radical

—CH₂—CH₂—S—S—CH₂—CH₂—;

d) an ureylene group of formula: —NH—CO—NH—.

Preferably, X⁻ is an anion such that chloride or bromide.

These polymers have a number average molecular weight ranging from 1000 to 100000.

Polymers of this type are notably disclosed in French patents 2,320,330, 2,270,846, 2,316,271, 2,336,434 and 2,413,907 and U.S. Pat. Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020.

One can more particularly used the polymers which are formed of repeating units of the following formula (VIII):

In which R₁₀, R₁₁, R₁₂ and R₁₃, identical or different, represent an alkyl ou hydroxyalkyl radical having 1 to 4 about carbon atoms, n and p are integers from 2 to about 20 and, X⁻ is an anion derived from a mineral or organic acid. One can in particular cite MEXOMERE PO commercialised by CHIMEX.

(11) The quaternary polyammoniums composed of repeating units of formula (IX:

wherein p is an integer from 1 to about 6, D can be absent or can represent a —(CH₂)_(r)—CO— group in which r is equal to 4 or 7, X⁻ is an anion

Such polymers can be prepared according to processes disclosed in U.S. Pat. Nos. 4,157,388, 4,702,906, 4,719,282. They are notably disclosed in patent application EP-A-122 324.

Among them, there can be for example cited, the products “Mirapol A 15”, “Mirapol AD1®”, “Mirapol AZ1®” and “Mirapol 175®” sold by Miranol.

(12) The quaternary polymers of vinylpyrrolidone and vinylimidazole such as Luviquat® FC 905, FC 550 and FC 370 by B.A.S.F.

(13) The polyamines like Polyquart® H sold by HENKEL, referenced under the name “POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE” CTFA dictionary, or the polyamines of oxyethylenated (15 OE) coprah.

(14) The crosslinked polymers of the methacryloyloxyalkyl(C₁-C₄) trialkyl(C₁-C₄)ammonium such as the polymers obtained through homopolymerization of dimethylaminoethylmethacrylate quaternized with methyl chloride, or through copolymerization of acrylamide with dimethylaminoethylmethacrylate quaternized with methyl chloride, the homo or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylene bis acrylamide. One can more particularly used a crosslinked acrylamide/methacryloyloxyethyl trimethylammonium (20/80 by weight) chloride copolymer in the form of a dispersion containing 50% by weight of said copolymer in mineral oil. This dispersion is commercialised under the name “SALCARE® SC 92” by ALLIED COLLOIDS. Crosslinked homopolymer of methacryloyloxyethyl trimethylammonium containing about 50% by weight of homopolymer in mineral oil or liquid ester can also be used. These dispersions are commercialised under the names “SALCARE® SC 95 and “SALCARE® SC 96” by ALLIED COLLOIDS.

Other cationic polymers usable within the frame of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers including vinylpyridine or vinylpyridinium units, condensates of polyamines and epichlorhydrine, quatenized polyureylenes and chitine derivatives.

Among all the cationic polymers that could be used in the frame of the present invention, it is preferred to use the polymers of families (1), (9), (10) (11) and (14) and even more preferably the polymers with repeating units of the following formulas (W) and (U):

and especially those having a molecular weight, as determined by gel permeation chromatography, of 9500 to 9900;

and especially those having a molecular weight, as determined by gel permeation chromatography, of about 1200.

The cationic polymer concentration in the reducing composition used in the process of the invention may vary from 0.01 to 10% by weight with regard to the total weight of the composition, preferably from 0.05 to 5% and still more preferably from 0.1 to 3%.

The amphoteric polymers optionally present in the reducing composition used in the process of the invention can be selected from polymers comprising K and M units statistically distributed within the polymer chain, where K represents a unit deriving from a monomer including at least one basic nitrogen atom and M represents a unit deriving from an acid monomer comprising one or several carboxylic or sulfonic groups, or else K and M can represent groups deriving from zwitterionic monomers of carboxybetains or sulfobetains;

K and M can also represent a cationic polymer chain including primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups bears a carboxylic or sulfonic group linked through a hydrocarbon radical, or K and M are part of a polymer chain with ethylene α,β-dicarboxylic unit wherein one of the carboxylic groups has been reacted with a polyamine including one or several primary or secondary amine groups.

The more particularly preferred amphoteric polymers corresponding to the above given definition are selected from the following polymers:

(1) The polymers resulting from the copolymerization of a monomer derived from a vinylic compound bearing a carboxylic group such as more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloracrylic acid, and a basic monomer derived from a substituted vinylic compound containing at least one basic atom such as more particularly the dialkylaminoalkylmethacrylate and acrylate, the dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are disclosed in american U.S. Pat. No. 3,836,537. One can also cite the copolymer sodium acrylate/acrylamidopropyl trimethyl ammonium chloride sold under the name POLYQUART® KE 3033 by HENKEL.

The vinylic compound can also be a dialkyldiallylammonium salt such as the dimethyldiallylammonium chloride. The copolymers of acrylic acid and of this latter monomer are proposed under the names MERQUAT® 280, MERQUAT® 295 and MERQUAT PLUS® 3330 by CALGON.

(2) The copolymers comprising units deriving from:

a) at least one monomer selected from acrylamides methacrylamides substituted on the nitrogen with an alkyl radical,

b) at least one acid comonomer containing several reactive carboxylic groups, and

c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents amine of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

The more particularly preferred N-substituted acrylamides or methacrylamides of the invention are groups whose alkyl radicals have 2 to 12 carbon atoms and more particularly N-ethylacrylamide, IN-tertiobutyl-acrylamide, N-tertiooctyl-acrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide as well as the corresponding methacrylamides.

The acid comonomers are more specifically selected from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as from the alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acid or anhydride.

The preferred basic comonomers are aminoethyl, butyl aminoethyl, N,N′-dimethylaminoethyl, de N-tertio-butylaminoethyl methacrylates.

There are particularly used copolymers whose CTFA (4ème Ed., 1991) name is Octylacrylamide/acrylates/butyl-aminoethylmethacrylate copolymer such as the products sold under the name AMPHOMER® or LOVOCRYL® 47 by NATIONAL STARCH.

(3) The crosslinked and partially or totally alkylated polyaminoamides deriving from polyaminoamides of general formula:

In which R₁₉ represents a divalent radical divalent derived from a saturated dicarboxylic acid, a mono or dicarboxylic aliphatic acid with ethylenic double bond, an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or a radical deriving from the addition of anyone of the said acids with a bis-primary or bis-secondary amine, and Z represents a radical of a bis-primary, mono or bis-secondary polyalkylene-polyamine and preferably represents:

a) in proportions of 60 to 100 moles %, the radical

where x=2 and p=2 or 3, or x=3 and p=2 this radical deriving from diethylene triamine, triethylene tétraamine or dipropylene triamine;

b) in proportions of 0 to 40 moles % the above radical (XI), in which x=2 and p=1 and which derives from the ethylenediamine, the radical deriving from the piperazine:

c) in proportions of 0 to 20 moles % the radical —NH—(CH₂)₆—NH— deriving from hexamethylenediamine, these polyaminoamines being crosslinked through the addition of a bifunctionnal crosslinking agent selected from epihalohydrines, diéepoxides, dianhydrides, bis insaturated derivatives, by means of 0.025 to 0.35 mole of crosslinking agent per amine group of the polyaminoamide and alkylated by the action of acrylic acid, chloracetic acid or an alkane sultone or their salts.

The saturated carboxylic acids are preferably selected among the acids having 6 to 10 carbon atoms such as the adipic, triméthyl-2,2,4-adipic and triméthyl-2,4,4-adipic, terephtalic acids, the acids with an ethylenic double bond such as for example the acrylic, methacrylic, itaconic acids.

The alkanes sultones used in the alkylation are preferably the propane or butane sultone, the salts of the alkylation agents are preferably the sodium or potassium salts.

(4) The polymers comprising zwitterionic units of formula:

In which R₂₀ is a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, R₂₁ and R₂₂ represent a hydrogen atom, methyl, ethyl or propyl, R₂₃ and R₂₄ represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R₂₃ and R₂₄ does not exceed 10.

The polymers comprising such units can also include units derived from non zwitterionic monomers such that dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.

As example, there can be cited the copolymer of methyl methacrylate/methyl dimethyl-carboxymethylammonio-ethylmethacrylate such as the product sold under the name DIAFORMER Z301 by SANDOZ.

(5) the polymers derived from chitosane comprising monomer units having the following formulas (XIII), (XIV), (XV):

unit (XIII) being present in proportions ranging from 0 to 30%, unit (XIV) being present in proportions ranging from 5 and 50% et unit F in proportions ranging from 30 and 90%, being understood that in this unit (XV), R₂₅ represents a radical of formula:

In which

when q=0, R₂₆, R₂₇ and R₂₈, identical or difference, represent each a hydrogen atom, a methyl, hydroxy, acetoxy or amino rest, a monoalkylamine or a dialkylamine rest optionally interrupted by one or several nitrogen atoms and/or et/ou optionally substituted with one or several amine, hydroxy, carboxy, alkylthio, sulfonic groups, an alkylthio rest the alkyl group of which bears porte an amino rest, at least one of radicals R₂₆, R₂₇ and R₂₈ being in this case a hydrogen atom;

or when q=1, R₂₆, R₂₇ and R₂₈ represent each a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

(6) The polymers derived from N-carboxyalkylation of chitosane such as the N-carboxymethyl chitosane or the N-carboxybutyl chitosane sold under the name “EVALSAN” by JAN DEKKER.

(7) The polymers of general formula (XI) such as those disclosed in French patent 1 400 366:

In which R₂₉ represents a hydrogen atom, a CH₃O, CH₃CH₂O, phenyl radical, R₃₀ is hydrogen or a lower alkyl radical such as methyl, ethyl, R₃₁ is hydrogen or a lower alkyl radical such as methyl, ethyl, R₃₂ is a lower alkyl radical such as methyl, ethyl or a radical of formula: —R₃₃—N(R₃₁)₂, R₃₃ representing a —CH₂—CH₂—, —CH₂—CH₂—CH₂—, —CH₂—CH(CH₃)— group, R₃₁ having the above mentioned meanings, as well as higher homologs of these radicals and containing up to 6 carbon atoms, and r is such that the molecular weight ranges from 500 to 6 000 000 and preferably from 1 000 to 1 000 000.

(8) Amphoteric polymers of the -D-X-D-X-type selected from:

a) the polymers obtained by action of chloracetic acid or sodium chloracetate de sodium son compounds comprising at least one unit of formula:

-D-X-D-X-D-  (XVII)

where D is a radical

and X is the E or E′ symbol, E or E′, identical or different, means a bivalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms within the main chain, non substituted or substituted with hydroxy groups and that may further include oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and/or heterocyclic cycles; the oxygen, nitrogen and sulphur atoms being present in the form of thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine, hydroxy, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane groups;

b) the polymers of formula:

-D-X-D-X-  (XVIII)

where D means a radical

and X is the E or E′ symbol and at least one time E′; E having the above indicated meanings and E′ is a bivalent radical which is an alkylene radical with is a straight or branched chain having up to 7 carbon atoms in the main chain, substituted or not with one or several hydroxy radicals and comprising one or several nitrogen atoms, the nitrogen atom being substituted with an alkyl chain optionally interrupted by an oxygen atom and necessarily including one or several carboxyl functions or one or several hydroxyl functions and et betainized through reaction with chloracetic acid or sodium chloracetate.

(9) The alkyl(C₁-C₅) vinylether/maleic anhydride partially modified by semiamidification with a N,N-dialkylaminoalkylamine such as N,N-dimethylamino-propylamine or by semiesterification with a N,N-dialkanolamine. These copolymers can also include other vinylic comonomers such as vinylcaprolactame.

The especially preferred amphoteric polymers according to the invention are those of family (1).

According to the invention, the amphoteric polymer(s) can represent 0.01% to 10% by weight, preferably 0.05% to 5% by weight, and even more preferred from 0.1% to 3% by weight, of the total weight of the reducing composition.

The anionic polymers possibly present in the reducing composition used in the process of the invention are polymers comprising groups derived from carboxylic, sulfonic or phosphoric acids, and having a 500 et 5 000 000.

The carboxylic groups are introduced by unsaturated carboxylic monoacids or diacids of formula:

In which n is an integer from 0 to 10, A′ is a methylene group, optionally linked to a à carbon atom of the unsaturated group or of the adjacent methylene group when n is higher than 1, through a heteroatom such as oxygen or sulfur, R₃₃ is a hydrogen atom, a phenyl or benzyl group, R₃₄R₃₃ is a hydrogen atom, a lower alkyl or carboxyl group, R₃₅ is a hydrogen atom, a lower alkyl group, a —CH₂—COOH, phenyl or benzyl group.

In above formula (XIX), a lower alkyl group comprises preferably 1 to 4 carbon atoms and in particular means, methyl and ethyl groups.

Invention preferred anionic polymers with carboxylic groups are:

A) the homo- or copolymers of acrylic or methacrylic acid or their salts, and in particular the products sold under the names VERSICOL® E or K by ALLIED COLLOID, ULTRAHOLD® by BASF. The acrylic and acrylamide acid copolymers sold in the form of their sodium salt under the names RETEN® 421, 423 or 425 by HERCULES, the sodium salts of polyhydroxycarboxylic acids.

B) the copolymers of acrylic or methacrylic acids with a monoethylenic monomer such as ethylene, styrene, vinylic esters, esters of acrylic or methacrylic acids, optionally grafted on a polyalkylene-glycol such as polyethylene-glycol, and optionally crosslinked. Such polymers are disclosed in particular in French patent 1 222 944 and German application no 2 330 956, copolymers of this type comprising in their chain an acrylamide unit optionally N-alkylated and/or hydroxyalkylated such as those disclosed in Luxemburg patent applications 75370 and 75371 or proposed under the name QUADRAMER® by AMERICAN CYANAMID. One can also cite the copolymers of acrylic acid and C₁-C₄ alkyl methacrylate and the copolymer of methacrylic acid and ethyl acrylate sold under the name LUVIMER® MAEX by BASF.

C) the copolymers derived from crotonic acid such as those comprising in their chain vinyl acetate or propionate units, and optionally other monomers such as the allylic or methallylic esters, the vinylic ether or the vinylic ester of a saturated carboxylic acid, linear or branched, with a long hydrocarbon chain, such that those comprising 5 carbon atoms, these polymers being possibly grafted or crosslinked, or still a vinylic, allylic or methallylic ester of a carboxylic α or β-cyclic acid. Such polymers are disclosed among others in French patents numbers 1 222 944, 1 580 545, 2 265 782, 2 265 781, 1 564 110 and 2 439 798. Commercial products within this class are 28-29-30, 26-13-14 and 28-13-10 sold by NATIONAL STARCH.

D) The polymers derived from maleic, fumaric, itaconic acids or anhydrides with vinylic esters, vinylic ethers, vinylic halogenides, phenylvinylic derivatives, acrylic acid and its esters; these polymers can be esterified. Such polymers are disclosed in particular in U.S. Pat. Nos. 2,047,398, 2,723,248, 2,102,113, GB patent 839 805, and those notably sold under the names GANTREZE® AN or ES by ISP.

Polymers also included in this class are copolymers of maleic, citraconic, itaconic anhydrides and an allylic or methallylic ester optionally comprising an acrylamide group, a methacrylamide group, an α-olefine, acrylic or methacrylic esters, acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions are monoesterified or monoamidified. These polymers are for example disclosed in French patents 2 350 384 and 2 357 241 of the applicant.

E) The polyacrylamides comprising carboxylate groups.

The polymers comprising sulfonic groups are polymers comprising vinylsulfonic, styrene-sulfonic, naphtalene-sulfonic or acrylamido-alkylsulfonic units.

These polymers can be in particular selected from:

the polyvinylsulfonic acid salts having a molecular weight ranging from about 1 000 to 100 000 as well as copolymers with an unsaturated comonomer such that acrylic or methacrylic acids, and their esters, and also acrylamide or its derivatives, the vinylic ethers and vinylpyrrolidone;

the salts of polystyrene-sulfonic acid, the sodium salts, having a molecular weight of about 500 000 and about 100 000 sold respectively under the names Flexan® 500 and Flexan® 130 by National Starch. These compounds are disclosed in patent FR 2198719;

the salts of polyacrylamide-sulfonic acids as those mentioned in U.S. Pat. No. 4,128,631, and more particularly the polyacrylamidoethylpropane-sulfonic acid sold under the name COSMEDIA POLYMER® HSP 1180 by Henkel.

The non-ionic polymers optionally present in the reducing composition used in the process of the invention can be selected from:

the vinylpyrrolidone homopolymers;

the copolymers of vinylpyrrolidone and vinyl acetate;

the polyalkyloxazolines such as the polyethyloxazolines proposed by DOW CHEMICAL under the names PEOX® 50 000, PEOX® 200 000 and PEOX® 500 000;

the homopolymers of vinyl acetate such as the products proposed under the name APPRETAN® EM by HOECHST or the product proposed under the name RHODOPAS® A 012 by RHONE POULENC;

the copolymers of vinyl acetate and acrylic ester such as the product proposed under the name RHODOPAS® AD 310 of RHONE POULENC;

the copolymers of vinyl acetate and ethylene such as the product proposed under the name APPRETAN® TV by HOECHST;

the copolymers of vinyl acetate and maleic ester, for example the dibutyl maleate such as the product proposed under the name APPRETAN® MB EXTRA by HOECHST;

the copolymers of polyethylene and maleic anhydride;

the homopolymers of alkyl acrylates and the homopolymers of alkyl methacrylates such as the product proposed under the name MICROPEARL® RQ 750 by MATSUMOTO or the product proposed under the name LUHYDRAN® A 848 S by BASF;

the copolymers of acrylic esters such that for example, the copolymers of alkyl acrylates and methacrylates as the products proposed by ROHM & HAAS under the names PRIMAL® AC-261 K and EUDRAGIT® NE 30 D, by BASF AS under the names ACRONAL® 601, LUHYDRAN® LR 8833 or 8845, by HOECHST under the names APPRETAN® N 9213 or N9212;

the copolymers of acrylonitrile and a non ionic monomer selected, for example, from butadiene and alkyl(meth)acrylates; there may be cited the products proposed under the names NIPOL® LX 531 8 by NIPPON ZEON or those proposed under the name CJ 0601 8 by ROHM & HAAS;

the polyurethans such as the products proposed under the names ACRYSOL® RM 1020 or ACRYSOL® RM 2020 by ROHM & HAAS, the products URAFLEX® XP 401 UZ, URAFLEX® XP 402 UZ by DSM RESINS;

the copolymers of alkyl acetate and urethan such as the product 8538-33 by NATIONAL STARCH;

the polyamides such as the product ESTAPOR® LO 11 proposed by RHONE POULENC;

the non ionic guar gums chemically modified or non modified.

The non ionic, non modified, guar gums are, for example, the products sold under the name VIDOGUM® GH 175 by UNIPECTINE and under the name JAGUAR® C by MEYHALL.

The non ionic, modified, guar gums, usable in the invention, are preferably modified by C₁-C₆ hydroxyalkyl groups. On peut mentionner à titre d'example, les groupements hydroxymethyl, hydroxyethyl, hydroxypropyl et hydroxybutyl.

These guar gums are well known in the art and can, for example, by reacting corresponding alkene oxides, such that, for example, propylene oxides, with the guar gum to obtain a guar gum modified by hydroxypropyl groups.

Such non-ionic guar gums optionally modified by hydroxyalkyl groups are, for example, sold under the trade-names JAGUAR® HP8, JAGUAR® HP60 et JAGUAR® HP120, JAGUAR® DC 293 and JAGUAR® HP 105 by MEYHALL, or under the name GALACTASOL® 4H4FD2 by AQUALON.

The alkyl groups of the non ionic polymers preferably comprise 1 to 6 carbon atoms.

The reducing composition used in the process of the invention can also contain one or several silicones.

The silicones possibly present in the reducing composition used in the process of the invention are in particular polyorganosiloxanes insoluble in the composition and can be in the form of oils, waxes, resins or gums.

The organopolysiloxanes are more precisely defined in Walter NOLL “Chemistry and Technology of Silicones” (1968) Academie Press.

The silicones can be volatile or non volatile.

When volatile, the silicones are more particularly selected among those having a boiling point ranging from 60° C. to 260° C., and still more specifically among:

-   -   (i) the cyclic silicones having 3 to 7 silicon atoms and         preferably 4 to 5.

They are, for example, the octamethylcyclotetrasiloxane commercialized notably under the name “VOLATILEE SILICONE 7207” by UNION CARBIDE or “SILBIONE 70045 V 2” by RHONE POULENC, the decamethylcyclopentasiloxane commercialized under the name “VOLATILEE SILICONE 7158” by UNION CARBIDE, “SILBIONE 70045 V 5” by RHONE POULENC, as well as their mixtures.

There can also be cited the cyclocopolymers of the dimethylsiloxanes/methylalkylsiloxane type, such as “SILICONE VOLATILEE FZ 3109” commercialized by UNION CARBIDE, of chemical structure:

There can also be cited the mixtures of cyclic silicones with silicon organic derivatives, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1′-(hexa-2,2,2′,2′,3,3′-trimethylsilyloxy) bis-neopentane;

(ii) the linear volatile silicones having 2 to 9 silicon atoms and a viscosity lower than or equal to 5.10⁻⁶ m²/s at 25° C. They are, for example, the decamethyltetrasiloxane commercialized in particular under the name “SH 200” by TORAY SILICONE. Silicones within this class are also disclosed in the article published in Cosmetics and toiletries, Vol. 91, Jan. 76, P. 27-32—TODD & BYERS “Volatile Silicone fluids for cosmetics”.

Preferably non volatile silicones are used and more specifically polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, polyorganosiloxanes modified with organofunctionnal groups as well as mixtures thereof.

These silicones are more particularly selected from polyalkylsiloxanes among which one can mainly cite the polydimethylsiloxanes with trimethylsilyl end groups having a viscosity of 5.10 to 2,5 m²/s at 25° C. and preferably 1.10⁻⁵ to 1 m²/s. The silicones viscosity is for example measured at 25° C. according to standard ASTM 445 Appendice C.

Among the polyalkylsiloxanes, there can be cited in a non limiting way the following commercial products:

the SILBIONE oils of the 47 and 70 047 series or the MIRASIL oils commercialized by RHONE POULENC such as for example the 70 047 V 500 000 oil;

the oils of the MIRASIL series commercialized by RHONE POULENC;

the oils of the 200 series by DOW CORNING such that more particularly the DC200 of viscosity 60 000 Cst;

the VISCASIL oils of GENERAL ELECTRIC and some oils of the SF (SF 96, SF 18) series of GENERAL ELECTRIC.

One can also cite the polydimethylsiloxanes with dimethylsilanol end groups (Dimethiconol according to CTFA designation) such that the oils of the 48 series by RHONE POULENC.

There can also be cited the polydimethylsiloxanes with aminoethyl, aminopropyl and alpha-omega silanol groups.

Within this class of polyalkylsiloxanes, there can also be cited the products commercialized under the names “ABIL WAX 9800 and 9801” by GOLDSCHMIDT which are polyalkyl(C₁-C₂₀) siloxanes.

The polyalkylarylsiloxanes are particularly selected among the polydimethyl-methylphenylsiloxanes, the linear or branched polydimethyl diphenylsiloxanes of viscosity of 1.10⁻⁵ to 5.10⁻² m²/s at 25° C.

Among these polyalkylarylsiloxanes one can cite for example the products commercialized under the following names:

the SILBIONE oils of the 70 641 series by RHONE POULENC;

the RHODORSIL oils of the 70 633 and 763 series by RHONE POULENC;

the DOW CORNING 556 COSMETIC GRAD FLUID oil by DOW CORNING;

the silicones of the PK series by BAYER as the product PK20;

the silicones of the PN, PH series by BAYER as the products PN1000 and PH1000;

some oils of the SF series by GENERAL ELECTRIC such as SF 1023, SF 1154, SF 1250, SF 1265.

The silicone gums possibly present in the reducing composition of the process of the invention are in particular polydiorganosiloxanes having high number average molecular weight ranging from 200 000 to 1 000 000 used alone or in mixture with a solvent. This solvent can be selected from volatile silicones, the polydimethylsiloxanes (PDMS) oils, the poly-phenylmethylsiloxanes (PPMS) oils, the isoparaffins, the polyisobutylenes, the methylene chloride, the pentane, the dodecane, the tridecanes or their mixtures.

There can be more particularly cite the following products:

polydimethylsiloxane,

polydimethylsiloxanes/methylvinylsiloxane gums,

polydimethylsiloxane/diphenylsiloxane,

polydimethylsiloxane/phenylmethylsiloxane,

polydimethylsiloxane/diphenylsiloxane/methylvinylsiloxane.

More specifically usable products are the following mixtures:

the mixtures formed from polydimethylsiloxane hydroxylated at the ends of the chain (named dimethiconol according to the CTFA dictionary nomenclature) and a cyclic poly-dimethylsiloxane (named according to the CTFA dictionary nomenclature) such that the product Q2 1401 commercialized by DOW CORNING;

the mixtures formed from polydimethylsiloxane with a cyclic silicone such that the product SF 1214 Silicone Fluid by GENERAL ELECTRIC, this product is a SF 30 gum corresponding to a dimethicone, having a number average molecular weight of 500 000 solubilized in the oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane;

the mixtures of two PDMS of different viscosities, and more particularly a PDMS and a PDMS oil, such as the product SF1236 by GENERAL ELECTRIC. The SF1236 product is a mixture of a SE 30 gum defined above having a viscosity of 20 m²/s and a SF 96 oil of viscosity 5.10⁻⁶ m²/s. This product comprises preferably 15% of SE 30 gum and 85% of a SF 96 oil.

The organopolysiloxanes resins optionally present in the reducing composition of the process of the invention are crosslinked siloxanic systems including units: R₂SiO_(2/2), R₃SiO_(1/2), RSiO_(3/2) and SiO_(4/2) in which R represents a hydrocarbon group having 1 to 16 carbon atoms or a phenyl group. Among these products, the particularly preferred ones are those in which R represents a C₁-C₄ lower alkyl radical, more specifically a methyl, or a phenyl radical.

Among these resins there can be cited the product commercialized under the name “DOW CORNING 593” or those commercialized under the names “SILICONE FLUID SS 4230 and SS 4267” by GENERAL ELECTRIC and which are silicones of dimethyl/trimethyl siloxane structure.

There can also be cited the resins of the trimethylsiloxysilicate type commercialized in particular under the names X22-4914, X21-5034 and X21-5037 by SHIN-ETSU.

The organomodified silicones optionally present in the reducing composition of the process of the invention are silicones such as previously defined and comprising in their structure one or several organofunctional groups linked by means of a hydrocarbon radical.

Among the organomodified silicones, there can be cited the polydiorganosiloxanes comprising:

polyethyleneoxy and/or polypropyleneoxy groups optionally comprising C₆-C₂₄ alkyl groups such that the products named dimethicone copolyol commercialized by DOW CORNING under the name DC 1248 or the oils SILWET L 722, L 7500, L 77, L 711 by UNION CARBIDE and the alkyl(C₁₂) methicone copolyol commercialized by DOW CORNING under the name Q2 5200;

substituted or non substituted aminated groups as the products sold under the names GP 4 Silicone Fluid and GP 7100 by GENESEE or the products sold under the names Q2 8220 and DOW CORNING 929 or 939 by DOW CORNING. The substituted or non substituted aminated groups are in particular C₁-C₄ aminoalkyl groups; there can be cited aminated silicones comprising alkoxy groups such as the silicone BELSIL AOM LOG 1 commercialized by WACKER;

thiol groups as the products commercialized under the names “GP 72 A” and “GP 71” by GENESEE;

alkoxylated groups as the product commercialized under the name “SILICONE COPOLYMER F-755” by SWS SILICONES and ABIL WAX 2428, 2434 and 2440 by GOLDSCHMIDT;

hydroxylated groups such as the polyorganosiloxanes with hydroxyalkyl function disclosed in French patent application FR-A-85 16334;

acyloxyalkyl groups such as the polyorganosiloxanes disclosed in U.S. Pat. No. 4,957,732;

anionic groups of the carboxylic type such as for example the products disclosed in patent EP 186 507 of CHISSO CORPORATION, or of the alkylcarboxylic type as those present in the product X-22-3701 E of SHIN-ETSU; 2-hydroxyalkylsulfonate; 2-hydroxyalkylthiosulfate as the products commercialized by GOLDSCHMIDT under the names “ABIL S201” and “ABIL S255”;

hydroxyacylamino groups, as the polyorganosiloxanes disclosed in application EP 342 834. Product Q2-8413 by DOW CORNING can for example be cited.

As non ionic silicone, there can be cited the block poly dimethylsiloxane/aminopolyether (80/20) polymer.

As previously explained, the process of the invention comprises an application step of an intermediate rinsing composition comprising at least one monovalent metallic cation salt and/or at least one ammonium salt, and at least one organic acid, the one or several monovalent salts not being one the salt(s) of the organic acid(s) present in the intermediate rinsing composition, and the salt(s) not being a surfactant.

By non surfactant salt, there is meant in the present invention a salt which does not contain an aliphatic fatty chain of at least 10 carbon atoms.

When the monovalent metallic cation salt(s) is (are) organic salt(s), the organic rest of the salt(s) contain generally less than 10 carbon atoms, better between 2 and 6.

Generally, the molecular weight of the salt(s) is (are) lower than or equal to 250 g/mol.

The monovalent metallic cation is preferably selected from the metal cations of column 1 of the periodic element classification and the Ag⁺ cation.

In a particular embodiment of the invention, the salt(s) included in the intermediate rinsing composition are mineral salts.

In particular there can be cited as salts included in the intermediate rinsing composition usable in the process of the invention sodium chloride NaCl, ammonium chloride NH₄Cl, potassium chloride KCl and silver chloride AgCl.

According to an other particular embodiment of the invention, the salt(s) included in the intermediate rinsing composition are organic salts.

There can be cited for example the ammonium organic salts, in particular ammonium citrate.

The salts included in the intermediate rinsing composition usable in the process of the invention can optionally be hydrated.

Generally, the salt(s) included in the intermediate rinsing composition represent from 0.1 to 20%, preferably from 0.1 to 10%, better from 0.5 to 8% by weight based on the total weight of the intermediate rinsing composition.

The organic acid(s) present in the intermediate rinsing composition are generally selected from acids comprising one or several carboxylic, sulfonic, phosphonic or phosphoric acid functions. They can contain other chemical functions in particular hydroxy or amino functions. They can be saturated or unsaturated.

There can be cited in particular the acetic, propanoic, butanoic, lactic, glycolic, ascorbic, maleic, phtalic, succinic acids, taurine and citric acid.

A preferred acid is citric acid.

The organic acid(s) represent generally from 0.005 to 10%, preferably from 0.01 to 1% by weight of the total weight of the intermediate rinsing composition.

In order to improve the cosmetic properties of the hair fibers or still to reduce or avoid their degradation, the intermediate rinsing composition used in the process of the invention can include one or several cosmetically active agents as those disclosed with the reducing composition.

According to a particular embodiment of the invention, the intermediate rinsing composition used in the process of the invention comprises one or several cationic, anionic, non-ionic or amphoteric polymers, and/or one or several silicones.

Preferably, the intermediate rinsing composition does not include amphoteric surfactant.

Still preferably, the intermediate rinsing composition does not include betain.

The pH of the intermediate rinsing composition generally ranges from 2 to 7, preferably from 3 to 5.

Preferably, the intermediate rinsing composition is to act for 30 seconds to 30 minutes.

As previously explained, the process of the invention comprises an application step of an oxidative composition.

The oxidative composition generally comprises at least one oxidative agent selected from hydrogen peroxide, alkaline bromates, polythionates, persalts, such as perborates, percarbonates and persulfates.

Preferably, the oxidative agent is hydrogen peroxide.

The oxidative agent(s) represent generally from 0.1 to 8%, preferably 0.2 to 5%, by weight with regard to the total weight of the oxidative composition.

Preferably, when the oxidative agent is hydrogen peroxide in aqueous solution, the oxidative composition used in the process of the invention contains a hydrogen peroxide stabilizing agent.

There can be cited the alkaline or alkaline earth metal pyrophosphates, such as tetrasodium pyrophosphate, alkaline or alkaline earth metal stannates, phenacetin or the salts of acids and oxyquinoleine, such as oxyquinoleine sulfate (8-hydroxyquinoleine sulfate). Still more advantageously, there is used at least one stannate in association or not with at least one pyrophosphate.

The hydrogen peroxide stabilizing agent(s) represent generally from 0.0001% to 5% by weight and preferably from 0.01 to 2% by weight with regard to the total weight of the oxidative composition.

In order to improve the cosmetic properties of the hair fibers or still to reduce or avoid their degradation, the oxidative composition used in the process of the invention can also include one or several cosmetically active agents, such as those previously mentioned in relation with the reducing composition.

Generally, the pH of the oxidative composition varies from 1 to 13, preferably from 1.5 to 8, better from 1.5 to 5.

The vehicle of the reducing, intermediate rinsing and oxidative compositions is preferably an aqueous medium made of water and can advantageously contain cosmetically acceptable organic solvents, more particularly, alcohols such as ethylic, isopropylic, benzylic, and phenylethylic alcohols, or polyols or polyol ethers such as, for example, glycerol, monomethylic, monoethylic and monobutylic ethers of ethyleneglycol, the propyleneglycol or its ethers such as, for example, the monomethyether of propyleneglycol, the butyleneglycol, the dipropyleneglycol as well as the alkylethers of diethyleneglycol as for example, the monoethylether op the monobutylether of diethyleneglycol. The organic solvents can be present in concentrations ranging from about 0.1 and 20% and, preferably, from about 1 and 1 0% by weight based on the total weight of the composition.

The pH of the reducing composition and the oxidative composition used in the process of the invention can be obtained and or adjusted classically through addition of either alkaline agents, such as for example ammoniaque, monoethanolamine, diethanolamine, isopropanolamine, 1,3-propanediamine, an alkaline or ammonium carbonate or bicarbonate, an organic carbonate such that the guanidine carbonate, or again an alkaline hydroxide, all these compounds being of course usable alone or in mixtures, or acidifying agents such as for example hydrochloric acid, acetic acid, lactic acid, boric acid, citric acid and phosphoric acid.

The reducing composition, the intermediate rinsing composition and the oxidative composition used in the process of the invention can independently be in the form of a lotion, a gel, a foam, a cream or a paste.

Las previously disclosed, the process of the invention comprises an application step of a reducing composition on keratinic fibers, in particular hair, an application step of an intermediate rinsing composition, then an application step of an oxidative composition.

According to a particular embodiment of the invention, the reducing composition application step and/or the intermediate rinsing composition application step and/or the oxidative composition application step are performed with heating or are immediately followed by heating.

Generally, the process of the invention comprises, after the oxidation fixing step, a rinsing step of the keratinic fibers with water and/or by means of a remaining portion of the intermediate rinsing composition.

When it is desired to realize a perm, mechanical means such as rollers are preferably used, the reducing composition being applied before, during or after the means for putting in form the hair, preferably after.

Preferably, the reducing composition is applied on wet hair previously rolled on rollers of 2 to 30 mm diameter. The composition can also be applied in the course of hair rolling. General, the reducing composition is maintained during a time of 5 to 60 minutes, preferably during 5 to 30 minutes.

It is also possible, after application of the reducing composition, subjecting the hair to a thermal treatment by heating at a temperature ranging from 30 to 250° C. during all or part of the pause time. In practice, this operation can be conducted by means of a cask, a hair dryer, a round iron or a flat iron, an infra-red rays dispensator and other heating apparatuses.

It can in particular be used, at the same time as a heating mean and a hair shaping means, a heating iron at a temperature ranging from 60 to 220° C., the use of the heating iron being made between the reducing composition application step and the intermediate rinsing application step.

The roller itself can be heating.

Thereafter there is applied, on the wet hair rolled and unrolled, the oxidative composition allowing keratin disulfide links reconstruction, generally during a pause time of 2 to 15 minutes. After withdrawal of the rolls, hair is generally abundantly rinsed, generally with water. The water rinsing may be replaced by rinsing with of a remaining portion of the intermediate rinsing composition, or pursue, following the water rinsing, with a rinsing with a remaining portion of the intermediate rinsing composition.

When hair uncurling or straighthening is desired, the reducing composition is applied on hair, then the hair is subjected to a mechanical deformation allowing fixing the hair in the new shape, through a smoothing operation of the hair with a large teeth comb, the back of a comb, hand or brush. Generally a pause time of 5 to 60 minutes, preferably 15 to 45 minutes is effected.

Hair smoothing can also be made, in all or part, with a heating iron at 60 to 220° C., and preferably at 120 to 200° C.

The intermediate rinsing composition as previously defined is thereafter applied on the hair. It is also possible to follow after this application with a heating treatment notably with an iron.

Then the oxidative composition as defined above is applied, and generally let to act during about 2 to 15 minutes, then the hair are generally abundantly rinsed, generally with water and/or with the remaining portion of the intermediate rinsing composition.

The permanent deformation process of the invention, in particular in the case of a rinsing at pH 3, presents, with regard to a simple rinsing step with water between the reduction step and the oxidation step, a protective effect of the artificial color of the hair, during implementation of the process as well as later after several washings with a shampoo.

Similarly, hair waving obtained during the permanent deformation of the hair by the process of the invention is better, as well as the unsticking of roots.

Finally, the presence in the process of the invention of an application step of an intermediate rinsing composition according to the invention improves also the cosmetic performances, such as gloss, smooth touch and ease of disentanglement of hair.

The invention is illustrated in a non-limiting manner by the following examples.

EXAMPLE 1

A reducing composition, an intermediate rinsing composition and an oxidative composition for implementing a hair permanent deformation process were prepared.

Formulations are as follows:

1. Reducing Composition

Thioglycolic acid 6.0% Ammonium bicarbonate 4.5% Mexomere PO 1.7% Oxyethylenated (20 moles of ethylene oxide) oleic 1.2% alcohol Mixture of cocoyl amidopropyl betaine/glyceryl mono- 1.4% laurate in aqueous solution at 30% Polydimethylsiloxane with aminoethyl aminopropyl and 2% alpha-omega silanols groups in cationic aqueous emulsion Diethylene triamine pentacetic acid, pentasodium salt 0.2% in aqueous solution at 40% Perfume 0.6% Demineralized water qsp 100 g %

2. Intermediate Rinsing Composition

Sodium chloride 5 g Citric acid 0.04 g pH 3 Demineralized water qsp 100 g

3. Fixing Composition

Hydrogen peroxide aqueous solution at 50% 4.8% (oxygenated water at 200 vol) 8-hydroxyquinolin sulfate 0.0125%   Sodium salicylate 0.01%  Poly di-methyl di allyl ammonium chloride in water 1.75%  at 40% not stabilized Lauryl dimethyl amine oxide in aqueous solution 2.15%  Vinylpyrrolidone/styrene copolymer in anionic 0.1% aqueous emulsion Lemon hydroglycolic extract alpha-hydroxyacids 0.1% content protected Perfume 0.4% Citric acid qsp pH 3 Demineralized water qsp 100 g %     

The reducing composition was applied on wet hair, previously rolled on rollers. The composition was left to act in contact with the hair for 10 minutes.

Then the intermediate rinsing composition was applied.

Thereafter the oxidative composition was applied on the hair. A pause of 5 minutes was maintained before rinsing with water and/or with the remaining portion of the intermediate rinsing composition.

EXAMPLE 2

A reducing composition (smoothing cream), an intermediate rinsing composition and an oxidative composition for implementing a hair permanent deformation process were prepared.

Formulations are as follows:

Smoothing Cream:

Thioglycolic acid 5.1% Diammonium dithiodiglycolate 2.5% Monoethanolamine 1.0% Ammonium bicarbonate 2.5% Behenyl trimethyl ammonium chloride in solution 2.0% In a water/isopropanol mixture Glycerol 2.0% Polyamine of oxyethylenated (15OE) coprah in aqueous 1.6% solution Oleic alcohol 3.0% Cetylic alcohol 6.0% Lanolin 1.0% Stearylic alcohol 2.5% Diethylene triamine pentacetic acid, pentasodium salt 0.4% In aqueous solution at 40% Perfume 1% Demineralized water qsp 100 g %

Intermediate Rinsing Composition

Sodium chloride 5 g Citric acid 0.04 g pH 3 Demineralized water qsp 100 g

Fixing Composition

Hydrogen peroxide aqueous solution at 50% 4.8% (oxygenated water at 200 vol) Monoethanolamide of alkyl (C13/C15 70/30 50% linear) 0.6% ether carboxylic acid (2 OE) Sodium Stannate 6 H₂O 0.04% Pyrophosphate tetrasodium, 10 H₂O 0.02% Homopolymer of methacrylate ethyl trimethyl 0.75% ammonium chloride crosslinked in reverse emulsion in mineral oil Glycerol 1.5% Polymer block poly dimethylsiloxane/aminopolyether 1.5% (80/20) in solution at 30% in dipropylene glycol Phosphoric acid 0.2% Mixture of cetylstearylic alcohol/ 2.0% oxyethylenated (30 OE) cetylstearylic alcohol Oleocetyl dimethyl hydroxyethyl 1.0% ammonium chloride in aqueous solution Perfume 0.4% Demineralized water qsp 100 g %

The smoothing cream was applied on wet hair and clean, then maintained in contact with the hair for 15 minutes.

Then the intermediate rinsing composition was applied on the hair.

The oxidative composition was thereafter applied, then maintained in contact with the hair to fix the given shape.

The hair was then rinsed with water and/or with the remaining portion of the intermediate rinsing composition.

EXAMPLE 3

In examples 1 and 2, sodium chloride can be replaced by ammonium chloride. Obtained results were similar. 

1. A process for permanently deforming keratinic fibers comprising: applying to said keratinic fibers a reducing composition, to reduce keratin disulfide linkages, the keratinic fibers being placed under mechanical tension before, during or after said application, then applying to said keratinic fibers an intermediate rinsing composition comprising at least one salt chosen from at least one salt of a monovalent metallic cation and at least one ammonium salt, and at least one organic acid, wherein said at least one monovalent salt is not a salt of said organic acid(s) present in the intermediate rinsing composition, and wherein neither the at least one monovalent salt nor the at least one ammonium salt is a surfactant, then applying to said keratinic fibers an oxidative composition in an oxidation fixing step to recreate said linkages, said process being free of any water rinsing step either between the reducing composition application step and the intermediate rinsing composition application step, or between the intermediate rinsing composition application step and the oxidative composition application step.
 2. A process according to claim 1, wherein said reducing composition is left to act for 5 to 60 minutes.
 3. A process according to claim 1, wherein said reducing composition comprises, in a cosmetically acceptable medium, at least one reducing agent selected chosen from reducing agents of formula: H(X′)_(q)(R′)_(r) in which X′ is chosen from P, S and SO₂, q is 0 or 1, r is 1 or 2 and R′ is a (C₁-C₂₀)hydrocarbon radical, linear or branched, saturated or unsaturated, optionally interrupted by an hetero atom, and optionally bearing substituents chosen from a hydroxy group, a halogenated group, an amine or a carboxy group, a ((C₁-C₃₀) alkoxy)carbonyl group, an amido group, a ((C₁-C₃₀)alkyl)amino carbonyl group, a (C₁-C₃₀)acyl)amino group, a mono or dialkylamino group, and a mono or dihydroxylamino group, or one of its salts in combination with a base.
 4. A process according to claim 3, wherein the at least one reducing agent is chosen from thioglycolic acid, thiolactic acid, glycerol monothioglycolate, cysteamine, N-acetyl-cysteamine, N-propionyl-cysteamine, cystein, N-acetyl-cystein, thiomalic acid, panthetein, 2,3-dimercaptosuccinic acid, N-(mercaptoalkyl)-ω-hydroxyalkylamides, N-mono or N,N-dialkylmercapto-4-butyramides, aminomercapto-alkylamides, derivatives of N-(mercaptoalkyl)succinamic acids and N-(mercaptoalkyl)succinimides, alkylamino mercaptoalkylamides, the azeotropic mixture of 2-hydroxypropyl thioglyconate and (2-hydroxy-1-méthyl)ethyl thioglycolate, mercaptoalkylaminoamides, N-mercapto-alkylalkanediamides and the derivatives of formamidine sulfinic acid, and salts thereof.
 5. A process according to claim 3, wherein the at least one reducing agent is present in an amount ranging from 0.05 to 30% by weight based on the total weight of the reducing composition
 6. A process according to claim 1, wherein the at least one salt is chosen from NaCl, NH₄Cl, KCl, and AgCl.
 7. A process according to claim 1, wherein the at least one salt is present in an amount ranging from 0.1 to 20% by weight based on the total weight of the intermediate rinsing composition.
 8. A process according to claim 1, wherein the at least one organic acid is chosen from acids comprising at least one functional group chosen from carboxylic, sulfonic, phosphonic and phosphoric acid functional groups.
 9. A process according to claim 8, wherein the at least one organic acid is chosen from acetic, propanoic, butanoic, lactic, glycolic, ascorbic, maleic, phtalic, succinic and citric acids.
 10. A process according to claim 1, wherein the at least one organic acid is present in an amount ranging from 0.005 to 10% by weight based on the total weight of the intermediate rinsing composition.
 11. A process according to claim 1, wherein said intermediate rinsing composition comprises at least one polymer chosen from cationic, anionic, non-ionic and amphoteric polymers, and/or at least one silicone.
 12. A process according to claim 11, wherein said intermediate rinsing composition does not contain betaine.
 13. A process according to claim 1, wherein said intermediate rinsing composition does not contain amphoteric surfactant.
 14. A process according to claim 1, wherein the pH of the intermediate rinsing composition ranges from 2 to
 7. 15. A process according to claim 1, wherein said oxidative composition comprises at least one oxidative agent chosen from hydrogen peroxide, alkaline bromates, polythionates, and persalts.
 16. A process according to claim 15, wherein the at least one oxidative agent is present in an amount ranging from 0.1 to 8% by weight with regard to the total weight of the oxidative composition.
 17. A process according to claim 1, wherein the pH of the oxidative composition ranges from 1 to
 13. 18. A process according to claim 1, wherein the intermediate rinsing composition is left to act for 30 seconds to 30 minutes.
 19. A process according to claim 1, wherein the reducing composition application step and/or the intermediate rinsing composition application step and/or the oxidative composition application step are performed with heating or are immediately followed by heating.
 20. A process according to claim 1, wherein it comprises, after the oxidation fixing step, a rinsing step of the keratinic fibers with water and/or by means of a remaining portion of the intermediate rinsing composition. 